US6355840B1 - Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt - Google Patents
Synthesis of permethyldodecaborate and paramagnetic dodecaborate salt Download PDFInfo
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- US6355840B1 US6355840B1 US09/576,842 US57684200A US6355840B1 US 6355840 B1 US6355840 B1 US 6355840B1 US 57684200 A US57684200 A US 57684200A US 6355840 B1 US6355840 B1 US 6355840B1
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- anion
- dianion
- borane
- trimethylaluminum
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- TVBISCWBJBKUDP-UHFFFAOYSA-N borate Chemical class [O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] TVBISCWBJBKUDP-UHFFFAOYSA-N 0.000 title abstract description 3
- 230000005298 paramagnetic effect Effects 0.000 title description 8
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 35
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000085 borane Inorganic materials 0.000 claims abstract description 16
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 16
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 abstract description 22
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 5
- 238000004607 11B NMR spectroscopy Methods 0.000 abstract description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 abstract description 3
- 238000010265 fast atom bombardment Methods 0.000 abstract description 3
- 238000004949 mass spectrometry Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 1
- CBWJKNQKWLEEPG-UHFFFAOYSA-N dihydridoborate(1-) Chemical compound [BH2-] CBWJKNQKWLEEPG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 23
- 241000894007 species Species 0.000 description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002000 high resolution fast-atom bombardment mass spectrometry Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- 229910015444 B(OH)3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000013175 Crataegus laevigata Nutrition 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910021537 Kernite Inorganic materials 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- SZKKRCSOSQAJDE-UHFFFAOYSA-N Schradan Chemical group CN(C)P(=O)(N(C)C)OP(=O)(N(C)C)N(C)C SZKKRCSOSQAJDE-UHFFFAOYSA-N 0.000 description 1
- LBZRRXXISSKCHV-UHFFFAOYSA-N [B].[O] Chemical group [B].[O] LBZRRXXISSKCHV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001730 borate mineral Inorganic materials 0.000 description 1
- 239000010429 borate mineral Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000004327 boric acid Chemical class 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000000155 isotopic effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- -1 methyl carbon Chemical compound 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
Definitions
- the present invention relates to unique three-dimensional methylated icosahedral boron cage compounds This invention was made with support under Contract Number DE-FG02-9ER61975 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
- Hawthorne et al has reported the preparation of closo-1,12-C 2 B 10 (CH 3 ) 12 and other octamethyl C 2 boranes.(Jiang, W., Knobler, C. B., Mortimer, M. D., Hawthorne, M. F., Angew. Chem ., 1995, 34, 1332.).
- the permethylated icosahedral carboranes [closo-CB 11 (CH 3 ) 12 ] 31 , and the uncharged blue radical closo-CB 11 (CH 3 ) 12 derived from that anion, has been reported by Michl et al. (King, B. T., Zanousek, B. G., Trammell, M., Noll. B. C., Michl, J., J Am. Chem. Soc ., 1996, 118, 3313) Additionally, other persubstituted polyboron compounds are known.
- the most prominent persubstituted polyboron compounds is the polyhydroxylated boron compound, boric acid, B(OH) 3 .
- Other common boron structures include the trigonal and tetrahedral boron-oxygen units common to borate minerals (G. A. Heller, Top. Curr. Chem .
- the charge-delocalized icosohedral ion [closo-B 12 H 12 ] 2 ⁇ may be considered as the parent aromatic species for borane chemistry in a manner similar to that served by the benzene ring in organic (carbon) chemistry.
- Isoelectronic substitution of one or two :B-H vertices in [closo-B 12 H 12 ] 2 ⁇ by :C-H + provides the aromatic derivatives [closo-1-CB 11 H 12 ] ⁇ , and a set of three isomeric dicarbacarboranes (1,2 ⁇ or ortho; 1,7 ⁇ or meta; and 1,12 ⁇ or para) closo-C 2 B 10 H 12 R (N.
- Paramagnetic persubstituted polyhedral closo-boranes such as [closo-B 6 X 6 ] ⁇ (Heinrich, A, Keller, H. L., Preetz, W. Z. Naturforsch., Mol B ., 1990, 45, 184) and [closo-B 9 X 9 ] ⁇ (Wong, E. H., Kabbani, R. M., Inorg. Chem ., 1990, 45, 184) where X is Cl, Br or I and [closo-CN 11 Me 12 ] ⁇ (B. T. King, B. T., Noll, B. C., McKinley, A. J., Michl, J., J. Am. Chem.
- FIG. 1 shows the molecular structure of the dodecamethyl-closo-dodecaborate(2 ⁇ ) anion [closo-B 12 (CH 3 ) 12 ] 2 ⁇ .
- FIG. 2 shows the molecular structure of the dodecamethyl-closo-dodecaborate(1 ⁇ ) anion [closo-B 12 (CH 3 ) 12 ] ⁇ .
- This method produced the permethyldodecaborate ion, [closo-B 12 (CH 3 ) 12 ] 2 ⁇ , dodecamethyl-closo-dodecaborate(2 ⁇ ) and the paramagnetic compound, [closo-B 12 (CH 3 ) 12 ] ⁇ when applied to the parent anion of the polyhedral borane family, aromatic [closo-B 12 H 12 ] 2 ⁇ .
- the anion and dianion were characterized by 1 H and 11 B NMR spectroscopy, high-resolution fast atom bombardment (FAB) mass spectrometry, cyclic voltammetry, and single-crystal X-ray diffraction.
- This procedure provides an alternate route to monoalkylated [closo-B 12 H 11 R] 2 ⁇ anions, which are usually obtained through palladium-catalyzed alkylation of [closo-B 12 H 11 I] 2 ⁇ with Grignard reagents (Peymann, T.; Knobler, C. B.; Hawthorne, M. F. Inorg. Chem . 1998, 37, 1544-1548). No reaction was observed when [PPh 4 ] 2 [closo-B 12 I 12 ] was heated for 4 days in neat trimethylaluminum at the reflux temperature.
- the dodecamethyl closo-borane anion [closo-B 12 (CH 3 ) 12 ] ⁇ can be produced by
- the structure was solved using statistical methods and refined by full-matrix least squares on F 2 .CCDC 182/1405. Crystallographic files are available in cif format at http://www.rsc.org/suppdata/cc/1999/2039/
- the B-B bond lengths of [closo-B 12 (CH 3 ) 12 ] 2 ⁇ are similar to the bond distances of the unsubstituted anion [closo-B 12 H 12 ] 2 ⁇ , reported by Wunderlich and Lipscomb (175.5(7)-178.0(7) pm (Wunderlich, J. A.; Lipscomb, W. N. J. Am. Chem. Soc . 1960, 82, 4427-4428).
- the B-C bond distances of [closo-B 12 (CH 3 ) 12 ] 2 ⁇ are longer than the B-C bond of [closo-B 12 H 11 (CH 3 ] 2 ⁇ , (158(2) pm; Peymann, T.; Knobler, C. B.; Hawthorne, M. F. Inorg. Chem . 1998, 37, 1544-1548), the exo B-C bonds of [closo-CB 11 (CH 3 ) 12 ] ⁇ (159(2)160.1(6) pm (King, B. T.; Janousek, Z.; Grüner, B.; Trammell, M.; Noll, B. C.; Michl, J., J. Am. Chem. Soc .
- the plane through the triangle B1, B4, and B5 is nearly parallel to the plane established by a pyridinium ring N1 and C2 through C6.
- the angle between the normals of these two planes is 7.3°.
- the distances of the boron atoms B1, B4, and B5 from the latter plane are 508(1), 486(1), and 504(1) pm, respectively and the distances of the methyl carbon atoms C1M, C4M, and C5M are 389(1), 338(1), and 378(1) pm, respectively.
- the radicals differ significantly in reactivity as their persistence largely depends upon the unpaired electron's chemical and physical environment. (Griller, D., Ingold, K. U., Acc.,Chem.Res , 1976, 9.13).
- a major effect that stabilizes paramagnetic species is steric crowding.
- a radical center surrounded by bulky groups is more persistent than similar species without this protection. This deep blue radical-anion is surprisingly stable with respect to reaction with oxygen.
- the crystal structure of the anion is shown in FIG. 2 .
- the anionic cluster of (Ph 3 P ⁇ N ⁇ PPh 3 ) [closo-B 12 (CH 3 ) 12 ] ⁇ is less distorted from icosahedral symmetry than the dianionic species [closo-B 12 (CH 3 ) 12 ] ⁇ studied as a [(Ph 3 P ⁇ N ⁇ PPh 3 )C 5 H 4 N) 2 CH 2 ] 2+ salt
- B-B bond lengths: [closo-B 12 (CH 3 ) 12 ] ⁇ 178.5(8)-180.5(7)pm;
- the maximum across-cage methyl carbon separations average 668 pm for the dianionic species compared to 663 pm for the monoanion.
- the greater distortion of [closo-B 12 (CH 3 ) 12 ] 2 ⁇ may be explained by the charge-transfer interaction of the dipositive [[closo-B 12 (CH 3 ) 12 ] (C 5 H 4 N) 2 CH 2 ] 2+ counter ion and the dianion. This interaction is suggested by the unique color of the blood-red [closo-B 12 (CH 3 ) 12 (C 5 H 4 N)CH 2 ] salt.
- [closo-B 12 (CH 3 ) 12 ] 2 ⁇ and the paramagnetic ion [closo-B 12 (CH 3 ) 12 ] ⁇ are weakly coordinated anions with lipophilic properties they are suitable for extraction of radioactive metal ions from nuclear waste.
- the [closo-B 12 (CH 3 ) 12 ] 2 ⁇ ion forms hydrocarbon soluble salts with cations such as cesium and strontium.
- [closo-B 12 (CH 3 ) 12 ] 2 ⁇ dissolved in kerosene or other hydrocarbon solvents can be used to extract 137 Cs + and 90 Sr 2+ from aqueous radioactive waste.
- a representative extraction formula, where M is the extracted metal, is as follows:
- the crude waste acid water phase is mixed with permethyldodecaborate salt.
- the hydrocarbon phase will then contain the complexed metal. Water was then mixed with the hydrocarbon phase to strip out the M 2+ and regenerate the H 3 O + salt dissolved in water.
- permethyldodecaborates can serve as precursors for new pharmacophores, resulting in new drugs. Still further, they can be used to produce stabilized unilamellar boron-containing liposomes for delivery to tumors for boron neutron capture therapy.
- the paramagnetic lipophilic anion because of its blue color and response to a magnetic or electric field, is further useful in sensor systems to detect easily oxidized or reduced compounds and, because it can function as an reversible electron trap (oxidant) could be incorporated in electrochemical systems.
- [closo-B 12 (CH 3 ) 12 ] ⁇ presents unique possibilities inherent in the concept of camouflaged polyhedral boranes.
- the persubstitution stabilizes an unusual oxidation state that has not been obtained from the ‘naked’ parent species [closo-B 12 H 12 ] 2 ⁇ .
- electrochemical oxidation E 1 ⁇ 2 1.43 V vs SCE
- the dianion instead dimerizes by an undetermined mechanism with loss of one exo H-atom and dimerization of B 12 -cages to form the B-H-B bridge of [B 24 H 23 ] 3 ⁇ (Wiersema, R. J., Middaugh, R. L., Inorg. Chem ., 1969, 8. 2074):
- a further advantage of the disclosed anions and there preparation are that they are easy to synthesize and therefore much less costly then prior available compounds such as produced by Michl.
- the anions disclosed herein are readily derived from (B 12 H 12 ) 2 ⁇ .
- the Michl species is expensive to make because it is derived from closo-(CB 11 H 12 ) ⁇ which is difficult, and therefore expensive, to produce.
- the water solubility of the resultant compounds provides a novel starting molecule for drug design.
- Other B n H n 2 ⁇ ions, for example B 10 H 10 2 ⁇ might be permethylated using the above described procedure.
- Metallocarborane and metalloborane anions are expected to undergo the same reactions and are possible substrates for methylation using this procedure, It is further contemplated that compounds such as N-bromo- or N-chlorosuccinimide could be used in the described procedure to produce a halomethyl derivative, such as [B 12 (CH 3 ) 11 CH 2 Cl] 2 ⁇ .
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Cited By (1)
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US9598352B2 (en) | 2011-11-18 | 2017-03-21 | The Curators Of The University Of Missouri | Process and device for the production of polyhedral boranes |
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Non-Patent Citations (6)
Title |
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J Am. Chem. Soc. by Peymann et al 121 pp. 5601-5602, year 1999.* |
M. Frederick Hawthorne, Broadening The Conflux of Boron and Carbon Chemistries,Dept. of Chemistry, University of California, Los Angeles, (presented in Durham, UK, Jul. 12, 1999), 8 pages. |
M.Frederick Hawthorbne, Carborane Chemistry At Work and At Play, Dept. of Chemistry and Biochemistry, The University of California, Los Angeles, (Presented at the Royal Society, UK 1996) pp. 1-17. |
Toralf Peymann, Carolyn B. Knobler, and M. Frederick Hawthorne, An Icosahedral Array of Methyl Groups Supported by an Aromatic Borane Scaffold: The [closo-B12(CH3 ) ]2-Ion, J. Am. Chem. Soc. May 29, 1999, 121, pp. 5601-5602. |
Toralf Peymann, Carolyn B. Knobler, and M. Frederick Hawthorne, An Unpaired Electron Incarcerated within an Icosahedral Borane Cage: Synthesis and Crystal Structure of the Blue, Air-stable {[colso-B12 (CH3) ]} radical, Chem. Commun., 1999, pp. 2039-2040. |
Wei Jiang, Carolyn B. Knobler, and M. Frederick Hawthorne, Decakis (dchloromethyl)-1, 12-dicarba-closo-dodecaborane (12): CAmouflage of an Icosahedral Carborane By Using Bulky Functional Substituents, Angew. Chem. Int. Ed. Eng 1, 1996, 35, No. 21, pp. 2536-2537. |
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US9598352B2 (en) | 2011-11-18 | 2017-03-21 | The Curators Of The University Of Missouri | Process and device for the production of polyhedral boranes |
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